Process of dyeing textile fibers



Patented Apr. .7, 1931 UNITED STATES PATENT OFFICE JEAN GEORGES KERN, OF WALTHAM, I MASSACHUSETTS, AND CHARLES J. SAL A, OI WILMINGTON, DELAWARE, ASSIGNORS TO E. I. DU POINT DE NEMOURS & OOMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OF DELAWARE PROCESS OF DYEING TEXTILE FIBERS No Drawing". Original application filed August 4, 1927, Serial No. 210,714. Divided and this application filed March 21, 1930. Serial N0. 437,936.

This case is a division of our copending application Serial No. 210,714, filed August 4, 1927.

This invention relates to alkylolamine salts a of aliphatic acids both saturated and unsaturated and to the sulfonic 'acid derivatives of these acid-s and more particularly to the ethanolamine salts of the higher fatty acids.

This invention has as objects the preparal tion of soluble oils, solvents and detergents as well as of antiseptic soaps.

These objects are accomplished by making the salts of the bases known as alkylolamines or hydroxy-alkylamines, more particularly of the ethanolamines, by combination with the fatty acids mentioned above by any of the Well known methods for the production of salts.

The bases used for our purpose may be rep- 20. resented by the following gene'r'al formula:

where Alk represents an alip'haticor hydroxy aliphatic radical, R and R represent hydrogen -or an aliphatic radical ora hydroxy aliphatic radical or a'poly hydroxy aliphatlc radical. In making these new soluble oils we may proceed as-follows:

The free fatty acids are combined directly with an organic base or a mixture of such.

bases. If the fatty acid is a solid the preparation is aided bythe application of heat. .It is also possible to start from the glycerides of the fatty acids, i. e., olive oil, cottonseed oil,

castor oil, linseed oil and the like by saponify-- ing the glycerides by heating with the base to a high temperature. In this case we find 40 that the reaction is complete when a sample of the mixture dissolves entirely in water. If water is present at the start this may be driven off, the base not being volatile, until a concentrated product is left behind. When making these products by this method it is found that an excess of base is necessary to give the most satisfactory results.

When preparing the products obtained from the sulfonated'fatty acids we may proceed as follows:

The acid product of the mixture of the sulfonated unsaturated acid as obtained by the action of sulfuric acid on an unsaturated oil such as castor oil in the well known manner is freed of mineral acid by washing. It is Example 2 1960 parts of oleic acid are mixed with 950 parts of a mixture containing tri-ethanolamine and 20% of di-ethanolamine. The products resulting from this procedure are semi-solids, particularly water soluble and ready for use without further treatment.

It is possible that the resultant material may.

be a compound of the base with the oleic acid but this has not been definitely established and is, in fact, immaterial to the success of the invention.

Example 3 298.37 parts of ricinoleic acid C '1H g(0H)CO0E are 10 mixed with parts di-ethanolamine. The resultant productis a clear yellow oil, very soluble in water.

Example 4 I 372 parts cantor all are mixed with 260 parts tri-ethmlamino 200 plrts Wlter.

The above mixture is heated on the water bath for several hours. The saponification proceeds slowly and in order to make it complete within reasonable time it is of advantage to add an excess, for example 30% tri-ethanolamine, above the quantity mentioned.

Example 5 284. 39 parts oflstearic acid are melted. Into the melt are stirrec 149 parts tri-ethanolamine,stirring is continued at a temperature of about 80 C. until the mixture is uniform.

The resultant product on cooling is a solid,

not very soluble 111 water but very soluble 1n alcohol. It acts as an excellent ass1stant in promoting solution.

Example 6 282 parts oleic acid 91 parts of amiuopropaue diol NH CI-I CHCH; OH

are heated together until completely mixed. The product is very soluble in alcohol. In water the solution is cloudy but becomes clear on the addition of some excess base, e. g. 15 to 20%.

Example 7 282 parts oleic acids are caused to react as given in the above example with 119 parts of methyl di-ethanolamine The soap obtained in this way has the property, when in alcoholic solution, of dissolving mercuric oxide and giving a relatively stable product soluble in Water. This is altogether a. surprising result and illustrates the use of these new soaps for pharmaceutical purposes.

Ewample 8 6 parts of a crude sulfonated oil made by the action of sulfuric acid on castor oil are mixed with 1' part of monoethanolam1ne.

Example .9

2T7 parts of a crude sulfonated oil mixture in the form of free acids are mixed with 1 part of a mixture of diand tri-ethanolamine The products of Examples 8 and 9 are entirely soluble in water. They are thlck yellow oils presumably containing salts of the bases of the sulfonic acids but this point has not been definitely established and is immaterial to the success of the invention. The products formed in this way are quite satisfactory for ordinary purposes.

In dyeing Ponsol blue GD double paste,

Schultz No. 842, on cotton yarn in the packmeaeaa Ewample 10 10 pounds caustic soda 15 pounds hydrosulfite concentrated. 10 pounds being added immediately and 5 pounds being added after one passage of the goods 100 gallons of water.

The temperature is raised to 110 F., and after complete reduction the dyeing started at this temperature. The temperature is then allowed to rise during 30 minutes to 125 6., and further dyed at this temperature for 10 to 15 minutes. Then give 1 wash, 4 passages in sodium perborate, 2 lbs. per 100 gals. at 120 F., 2 cold washes, 5 passes in boiling soap solution 3 lbs. soap to 100 gallons. then rinse and wash in the open, dry and calender.

This example, illustrating the method of dyeing, is similar to Example 1 given in copending application Serial No. 210.715, filed by applicants on August 4, 1927. The difference between this example and the said Example 1 lies in the substitution of the novel assistants herein disclosed by applicants.

Example 11 The new compounds described in this ap- I ufacture of Ponsol blue GD, Schultz No. 842,

is converted into a press cake containing 30% of dry color. 400 parts of the press cake are then mixed with 20 parts of glycerine and 580 parts of one of the assistants prepared according to Examples 1 to 9 and Example 13 of this application. It is possible to vary the quantities considerably without losing the advantages of this invention.

E trample 12 The new compounds described in this case 4 may be used in printing pastes. containing lakes of basic colors. The mode of procedure 1n using such a printing paste is illustrated in the .followlng example:

10 parts basic polor (suitable for discharge printing) 50 parts glyecrlne 50 parts of anyone of the products described in Examples l to 9 and Example 13 of this application 200 parts water 580 parts thickening composed of starch or gums and a certain amount of sodium hydrosullite formaldehyde necessary to cut the ground parts tannin dissolved in equal parts of water or alcohol.

' If a pure product is needed the operation may be carried out as follows:

378 parts of pure sulfo-ricinoleic acid prepared by the action of chlorosulfonic acid on pure ricinoleic acid are mixed with r 149 parts of tri-ethanolamine.

In the above case the addition of a further molecular equivalent of base produces a more soluble oil. The reason may be that the extra quantity of base combines with the carboxyl group but again termined.

In the above examples any one of the bases as defined by the general formula given above may be used either alone or in mixture. The fatty acids may also be varied through a wide range.-

By the term alkylol. as used herein, we mean to include an alkyl radical in which one or more hydrogens are replaced by a this point has not been de- 'hydroxyl group, and may be represented by the following o..nz...orr or -c..H.. 1 (on 2.

We have found that these products, which are essentially organic soaps possess a greater dissolving power or dispersing power for organic substances than do ordinary soaps. They possess the detergent property I of soaps without the high alkalinity characteristic of sodium or potassium salts of the fatty acids. These products for these reasons have a distinct advantage for many purposes and particularly as assistants in dyeing, and'these compounds which are derived- -from sulfonated castor Oll by the process mentioned are in many ways superior to ordinary sulfonated oils. evidenced by the greater evenness of the shades developed, the better utilization of the color, and the greater brilliance of the dyeing.

\Vhen added to water they bring about solution or dispersion in so fine a form as to appear a solution of insoluble organic bases such as amino-azo-benzene, para-nitro-benzene, azo-diphenyl-amine, benzene-aZo-naphthalene-aZo-phenol, Rosanthrene base, diethyl-para-amido-phenol-l 4 naphtho-quinone-mono-imide, 2.4: di-nitro-benzene-l-azodi ethyl-aniline, etc. ,It takes about 2 to 5 arts of the solvent for 1 part of the insolule base. These solutions may be used very Their superiority is successfully for the purpose of dyeingfibers solve metallic hydroxides and oxides, for example, mercuric oxide, and this property indicates their probable value in pharmacology, for example, in the production of antiseptic soaps and the like.

As many apparently widely different enibodiments of this invention may be made without departing from the spirit thereof, it is to be understood that we do not intend to limit ourselves to the specific embodiments thereof except as indicated in the appended claims.

WVe claim: i

1. In a process of applying a dye to textile fibers, the step which comprises mixing with said dye a product resulting from the chemical combination of stearic acid and an alkylolamine.

2. In a process of applying a dye to textile said dye a product resulting from the chemical combination of stearic acid and a substance of the group consisting of mono= ethanolamine, di-ethanolamine, tri-ethanolamine and amino-propane diol.

4. In a process of applying a dye to textile fibers, the step which comprises mixing with said dye a product resulting from the chemical combination of stearic acid and at least one of the substances from the group consisting of di-ethanolamine and tri-ethanolamine.

5. In a process of applying a dye to textile fibers, the step which comprises mixing with said dye a product resu ting from the chemical combination of s ear'ic" acid arfd triethanolamine.

6. In a process of applying a dye to textile fibers. the step which comprises mixing with said dye a product resulting from the'chemical combination of stearic acid and a compound having the following formula:

in which Alk represents an aliphatic or hydroxy aliphatic radical, while both R and fibers, the step which comprises mixing with said dye a product resulting from the chemical combination of stearic acid and diethanolamine.

9. In a process of applying a dye to textile fibers, the step which comprises mixing with said dye a product resulting from the chemical combination of stearic acid and monoethanolamine.

In testimony whereof We afiix our signatures.

JEAN GEORGES KERN. CHARLES J. SALA. 

